EP2664683B1 - Process for producing a mesoporous carbide - Google Patents

Process for producing a mesoporous carbide Download PDF

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Publication number
EP2664683B1
EP2664683B1 EP12168207.4A EP12168207A EP2664683B1 EP 2664683 B1 EP2664683 B1 EP 2664683B1 EP 12168207 A EP12168207 A EP 12168207A EP 2664683 B1 EP2664683 B1 EP 2664683B1
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European Patent Office
Prior art keywords
alloy
phase
amorphous
mesoporous
heat treatment
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EP12168207.4A
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German (de)
English (en)
French (fr)
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EP2664683A1 (en
Inventor
Pere Bruna
Maria Jazmin Duarte-Correa
Julia Lengsfeld
Frank Uwe Renner
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Max Planck Institut fuer Eisenforschung
Universitat Politecnica de Catalunya UPC
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Max Planck Institut fuer Eisenforschung
Universitat Politecnica de Catalunya UPC
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Priority to ES12168207.4T priority patent/ES2686928T3/es
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/003—Making ferrous alloys making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2201/00—Treatment for obtaining particular effects
    • C21D2201/03—Amorphous or microcrystalline structure

Definitions

  • Present invention relates to a process for producing a mesoporous carbide wherein an amorphous alloy is subjected to a heat treatment and a chemical and/or electrochemical process, to a mesoporous carbide which is obtainable according to such process, to the use of the mesoporous carbide as catalyst or support material for a catalyst and to a crystallized steel obtainable from the amorphous steel alloy.
  • Mesoporous materials present a large surface-to-volume ratio providing sites for catalysis, molecular separation, adsorption or chemical sensing.
  • Some of the classical mesoporous materials employed include silica, alumina, zirconia, zeolites, and other diverse oxides such Ti or Co, and they are synthetized by routes as self-assembly, sol-gel, spray drying and some variations of these methods known in the state of the art.
  • some elements of the platinum group such as Pd, Ru, and their alloys are broadly used and investigated, also as thin films on mesoporous supports to achieve lower costs or superior stability. Transition metals such Fe represent a cheaper option with high catalytic properties.
  • One of the reasons that iron or its alloys are not considered for this purpose is its low environmental and thermal stability.
  • Subject of present invention is therefore a process, as defined in the claims, for producing a mesoporous carbide having a pore size between 10 nm to 70 nm, wherein an amorphous alloy consisting of in atomic percent Fe a Cr b Mo c C d B e wherein
  • a further subject of present invention is a mesoporous carbide obtainable according to the process mentioned above.
  • the amorphous alloy is used as a precursor.
  • the crystallization of the amorphous alloy results in the formation of a fine structure comprising crystals in a nanometer range.
  • M M 23 C 6 carbides
  • an amorphous alloy having a composition consisting of Fe a Cr b Mo c C d B e , wherein a, b, c, d and e are as defined above is used as a starting material.
  • Good results of crystallization and subsequent formation of the mesoporous structure are obtained with an alloy wherein the ratio of (a + b + c) : (d + e) is from 3 : 1 to 6.5 : 1, and the ratio of b : c is from 1.2 : 1 to 1 : 1.2.
  • the alloy used as starting material may comprise unavoidable impurities such as O, Si, Ti and/or Cu.
  • amorphous alloy is subjected to a heat treatment in order to obtain a crystalline fraction above 50 % in the alloy.
  • the heat treatment includes initial devitrification, i. e. formation of crystals with a maximum size of approximately 50 nm by annealing the starting material at high temperatures.
  • the range of temperatures for crystallization of the amorphous alloy can be assessed by Differential Scanning Calorimetry (DSC).
  • DSC Differential Scanning Calorimetry
  • the heat treatment is preferably carried out at a temperature range above the second crystallization temperature, if the amorphous alloy shows more than two crystallization temperatures, and the melting temperature.
  • the heat treatment is carried out between 600 °C and 1000°C, preferably between 650°C and 1000°C.
  • the amorphous alloy used as a starting material may be obtained by a rapid quenching process, preferably from a melt spinning process or casting process, for example into copper mold, or by coating processes, as thermal spraying or physical vapor deposition of the alloy onto a support material or substrate.
  • the product from the heat treatment is subjected to a chemical and/or electrochemical treatment.
  • the chemical and/or electrochemical weak phases of the crystallized alloy are dissolved leading to the mesoporous structure.
  • the chemical treatment can be carried out by immersing the heat treated material into an acidic or basic solution, for example with a strong acid such as HCI, HNO 3 , H 2 SO, or any mixture of them such as aqua regia.
  • the electrochemical treatment of the crystallized alloy can be performed with either galvanostatic polarization or potentiostatic polarization. For the galvanostatic polarization the current is kept constant; typical values are 70-80 ⁇ A, dependent on the sample size.
  • the potentiostatic polarization is carried out with a constant potential which is selected at the breakdown potential of the material.
  • Typical values for the Fe a Cr b Mo c C d B e starting alloy are 430-480mV vs. a standard hydrogen electrode.
  • a further subject of present invention is a mesoporous carbide which is obtainable by the process described above.
  • the product from the chemical and/or electrochemical treatment is a mesoporous material having a pore size between 10 nm and 70 nm, preferably between 20 nm to 60 nm.
  • the mesoporous structure may be present on the surface of the alloy or the alloy may be percolated by the pores, i. e. has the structure of a sponge.
  • the mesoporous carbide has the form of a film, sheet, plate, bar or in the form of particles, the surface of each of these films shows the mesopores.
  • the mesoporous carbide according to present invention may be used as a catalyst or as a support material for a catalyst.
  • a further subject of present invention is therefore a crystallized metallic glass having the composition consisting of in atomic percent Fe a Cr b Mo c C d B e wherein
  • the crystallized metallic glass shows a crystalline fraction of above 50 % of the total form of the alloy.
  • the crystallized fractions comprise preferably main phases (Fe, Cr, Mo) 23 (C,B) 6 and (Fe,Mo) 6 C, with M 7 C 3 and alpha-Fe in minor concentration.
  • Amorphous ribbons of Fe 50 Cr 15 Mo 14 C 15 B 6 (at.%) were prepared by melt spinning with a speed of 40 m/s ( H. H. Liebermann, IEEE Transactions on Magnetics, 1976, 12, 921 ; A. L. Greer, Science, 1995, 267, 1947 ).
  • the glass transition temperature (T g 550 °C)
  • Crystallization of the amorphous alloy was then induced by thermal annealing in argon atmosphere at 620 °C, 650 °C, 670 °C and 800 °C for 20 min to obtain partially and fully crystalline conditions.
  • the amorphous state and the lack of long range order in the as-quenched alloy are evidenced by the respective X-ray diffractogram displayed in Figure 2 .
  • XRD measurements using a monochromatic Cu K ⁇ radiation (Bruker AXS) were set up in 2 ⁇ angle in the range of 10-110° with a step size of 0.05°.
  • the pattern of the as-quenched ribbons shows the broad diffuse peaks characteristic of the amorphous alloys.
  • the signals at 620 °C point to a composite structure of crystalline carbides in an amorphous matrix.
  • a M 7 C 3 phase is also present in these intermediate states.
  • the sample is considered fully crystallized.
  • the relatively sharp Bragg peaks at this last state indicate the presence of two main nano-crystalline phases, identified by correlated analysis with Atom Probe Tomography (APT) as (Fe,Cr) 23 (C,B) 6 and ⁇ -Fe 3 Mo 3 C.
  • APT Atom Probe Tomography
  • APT analyses were performed using a local electrode atom probe (Imago LEAPTM 3000X HR) in voltage mode at 200 kHz pulse frequency, with a pulse fraction of 15% for a detection rate of 0.5%.
  • the specimen base temperature was 60 K.
  • APT specimens were prepared using a FEI Helios Nanolab 600 dual-beam focused ion beam as described in K. Thompson, D. Lawrence, D. J. Larson, J. D. Olson, T. F. Kelly, B. Gorman, Ultramicroscopy, 2007, 107, 131 ; M. K. Miller, K. F. Russell, G. B. Thompson, Ultramicroscopy, 2005, 102, 287 .
  • Mo is increasingly enriched in the amorphous matrix (red areas in the reconstruction at 620 °C) until finally a secondary crystalline Mo-rich M 6 C phase is nucleated, highlighted by the isoconcentration surfaces at 22 at. % Mo in Figure 3 at 650 °C.
  • Figure 3 shows the elemental mapping of Fe atoms for the sample annealed at 800 °C together with isoconcentration surfaces for 15 at. % of Cr and 32 at. % of Mo.
  • Mo-rich and Cr-rich phases of size up to 50 nm, are clearly visible and their boundaries are indicated by the isoconcentration surfaces.
  • composition of the Cr-rich region is in agreement with the (Fe,Cr) 23 (C,B) 6 phase identified by XRD, with a small amount of Mo atoms partially substituting some of the original metals.
  • composition of the M 6 C phase corresponds to the data obtained from the Mo-rich region, with a small concentration of boron taking the place of carbon atoms.
  • Annealing and crystallization at 800 °C then leads to concentrations of the two above main phases very close to the equilibrium predicted by thermodynamic calculations. Most important, a percolation of both crystalline phases throughout the fully crystallized sample is clearly visible.
  • SAEM Scanning Auger Electron Microscopy
  • Auger electron maps were recorded with a scanning Auger microprobe (Jeol JAMP-9500F).
  • Figure 4A shows SAEM overlaying maps of O and N after heat treatment at 800 °C.
  • a more detailed analysis of the Fe and Cr signatures of the recorded scans revealed the presence of Fe 2 O 3 and Cr 2 O 3 as main oxide components of the surface layer, while nitrogen, in smaller concentration, tends to form compounds with molybdenum.
  • the corrosion behavior of the alloy at the different stages of crystallization was analyzed by electrochemical linear polarization sweeps in the anodic (positive) direction, in 0.1 M HCI solution, Figure 4C .
  • Electrochemical measurements were performed using a scanning droplet cell with gold as counter electrode and a micro Ag
  • Open circuit potential measurements were recorded for 100sec in 0.1 M HCI followed by linear polarization curves (in positive direction) starting -0.3 V with a scan rate of 2 mVs-1 at ambient pressure and temperature. All potentials were then referred to SHE.
  • the fully amorphous alloy passivates spontaneously and shows the largest passivation range. Passivation occurs at low current density (less than 50 ⁇ A cm -2 ) only slightly higher than the presented by pure Cr, when compared in the plot.
  • the breakdown potential reaches 1.1 V vs. SHE, linked to the massive dissolution of the elements present in the alloy, thus showing a highly protective film against acid solutions.
  • An increasing annealing temperature to 620 °C leads to a moderately larger passive current and an initial dissolution peak with a clearly higher intensity than the as-quenched material.
  • the polarization curve of the sample annealed at 650 °C presents rather a pseudopassive polarization curve with a breakdown potential near the fully amorphous state about 1.1 V.
  • phase separation and crystallization in the Fe 50 Cr 15 Mo 14 C 15 B 6 metallic glass causes formation of Mo-rich zones with low concentration of Cr, and this more unstable phase will dissolve preferentially.
  • An interconnected network morphology as observed in the APT reconstructions at annealing temperature of 800°C ( Figure 3 ), would generate dissolution throughout the material causing an early breakdown.
  • weak Mo-rich regions initiate the corrosion process.
  • smaller crystal sizes, lack of percolation, and the remaining presence of the amorphous state block the dissolution.
  • TEM Scanning Transmission Electron Microscopy
  • EDX Energy Dispersive X-ray Spectroscopy
  • TEM specimens were prepared from regions of interest using a FEI Helios Nanolab 600 dual-beam focused ion beam system operated at 30 kV. To minimize the effects of Ga ions beam damage, the final milling of the specimens was conducted at low ion energies (5 kV).
  • TEM was performed using a Jeol JEM-2200FS operated at 200kV and equipped with Jeol EDX system for chemical analysis. Images with a high atomic number contrast were acquired using a high angle annular dark field (HAADF) detector in STEM mode.
  • HAADF high angle annular dark field
  • the dissolution of the Mo-rich phases after crystallization were performed with either galvanostatic polarization or potentiostatic polarization.
  • galvanostatic polarization a constant current is applied to the sample with usual values of 70-80 ⁇ A, dependent on the sample size.
  • potentiostatic polarization a constant potential is applied with an usual voltage of 430-480mV vs. SHE, the potential is selected at the breakdown potential of the material.
  • the sample is immersed in the acid or basic solution (0.1M HCl or 0.1 M H 2 SO 4 for example) and the potential or current are applied for a defined period of time at the conditions explained before(typical immersion time is 1000-4000sec). With increasing immersion time the depth of the mesoporous structure will increase.
  • the electrochemical measurements were carried out using a three electrode setup, where the sample is connected as working electrode, graphite and Ag/AgCl are used as counter electrode and reference electrode, respectively (any other counter and reference electrodes work as well).

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EP12168207.4A 2012-05-16 2012-05-16 Process for producing a mesoporous carbide Active EP2664683B1 (en)

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EP12168207.4A EP2664683B1 (en) 2012-05-16 2012-05-16 Process for producing a mesoporous carbide
ES12168207.4T ES2686928T3 (es) 2012-05-16 2012-05-16 Proceso para la producción de un carburo mesoporoso

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EP2664683A1 (en) 2013-11-20

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